Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
  • C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
  • C08F210/18—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers with non-conjugated dienes, e.g. EPT rubbers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F4/00—Polymerisation catalysts
  • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
  • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
  • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
  • C08F4/62—Refractory metals or compounds thereof
  • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
  • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F2420/00—Metallocene catalysts
  • C08F2420/02—Cp or analog bridged to a non-Cp X anionic donor
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F2420/00—Metallocene catalysts
  • C08F2420/04—Cp or analog not bridged to a non-Cp X ancillary anionic donor
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F4/00—Polymerisation catalysts
  • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
  • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
  • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
  • C08F4/62—Refractory metals or compounds thereof
  • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
  • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
  • C08F4/65908—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an ionising compound other than alumoxane, e.g. (C6F5)4B-X+
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F4/00—Polymerisation catalysts
  • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
  • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
  • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
  • C08F4/62—Refractory metals or compounds thereof
  • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
  • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
  • C08F4/65912—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an organoaluminium compound
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10S526/00—Synthetic resins or natural rubbers -- part of the class 520 series
  • Y10S526/943—Polymerization with metallocene catalysts

Definitions

• the invention relates to a process for the preparation of a polymer comprising monomeric units of ethylene, an ⁇ -olefin and a vinyl norbornene.
• the invention also relates to a polymer obtainable by the process of the invention.
• Such a process and polymer are known from EP-A-765908 .
• a polymer consisting of ethylene, propylene and vinyl norbornene is described as well as various processes for the production the polymer.
• An advantage of the polymer comprising the monomeric units of vinyl norbornene is that it cures fast and to a high level when using a peroxide as a curative. For that reason it is desirable to use the polymer in rubber composition suitable for peroxide curing, like for instance rubber compositions used for the production of cable and wire, hoses for automotive applications, like for instance radiator hoses and hoses used in the braking system, thermoplastic elastomers and a wide variety of further rubber applications.
• a serious disadvantage however is that in the production of the polymer comprising the vinyl norbornene using one of the known processes is that a high amount of branches is formed in the polymer and sometimes even gelation of the polymer takes place. Due to the high amount of branches the polymer has a broad molecular weight distribution. This is a disadvantage for the mechanical properties of a rubber comprising the polymer. If gelation occurs the polymer is partly or entirely crosslinked. The gelation is disadvantageous, as it causes the polymerization process to be unstable, reactor fouling to take place and the polymer to be not useful for use in a rubber composition intended for the production of shaped articles.
• Object of the invention is to provide a process for the preparation of a polymer comprising monomeric units of ethylene, an ⁇ -olefin and a vinyl norbornene, the polymer showing less branches in terms of the dynamic mechanical quantity ⁇ , defined in the following, and no or at least decreased risk for gelation.
• the polymer comprising the monomeric units of ethylene, the ⁇ -olefin and the vinyl norbornene shows considerable less long chain branching and no or hardly any gelation.
• a further advantage is that in the polymer obtained with the process according to the invention a larger portion of the vinyl norbornene is polymerized with only one of the two double bonds, the second double bond being available for the curing of the polymer. This results in a polymer being even more reactive to peroxide curing.
• aluminoxane is used as the sole activating compound.
• the catalyst used in the process according to the invention preferably contains a phosphinimine ligand which is covalently bonded to the metal.
• This ligand is defined by the formula: wherein each R 1 is independently selected from the group consisting of a hydrogen atom, a halogen atom, C 1-20 hydrocarbyl radicals which are unsubstituted by or further substituted by a halogen atom, a C 1-8 alkoxy radical, a C 6-10 aryl or aryloxy radical, an amido radical, a silyl radical of the formula III, and a germanyl radical of the formula IV:
• This ligand contains a "mono substituted nitrogen atom" in the sense that there is only one phosphorus atom (doubly) bonded to the nitrogen atom.
• the preferred phosphinimines are those in which each R' is a hydrocarbyl radical.
• a particularly preferred phosphinimine is tri-(tertiary butyl) phosphinimine (i.e. where each R' is a tertiary butyl group).
• ketimide ligand refers to a ligand which: (a) is bonded to the transition metal via a metal-nitrogen atom bond; (b) has a single substituent on the nitrogen atom, (where this single substituent is a carbon atom which is doubly bonded to the N atom); and (c) preferably has two substituents (Sub 1 and Sub 2 , described below) which are bonded to the carbon atom as illustrated in Form. VIII.
• This ligand also contains a mono substituted nitrogen atom in the sense that only one carbon atom is (doubly) bonded to the nitrogen atom.
• substituents "Sub 1 " and “Sub 2 " may be the same or different.
• substituents include hydrocarbyls having from 1 to 20 carbon atoms; silyl groups, amido groups and phosphido groups.
• cyclopentadienyl ligand is meant to broadly convey its conventional meaning, namely a ligand having a five carbon ring which is bonded to the metal via eta-5 bonding.
• cyclopentadienyl includes unsubstituted cyclopentadienyl, substituted cyclopentadienyl, unsubstituted indenyl, substituted indenyl, unsubstituted fluorenyl and substituted fluorenyl.
• An exemplary list of substituents for a cyclopentadienyl ligand includes the group consisting of C 1-10 hydrocarbyl radical (which hydrocarbyl substituents are unsubstituted or further substituted); a halogen atom, C 1-8 alkoxy radical, a C 6-10 aryl or aryloxy radical; an amido radical which is unsubstituted or substituted by up to two C 1-8 alkyl radicals; a phosphido radical which is unsubstituted or substituted by up to two C 1-8 alkyl radicals; silyl radicals of the formula III and germanyl radicals of the formula IV:
• the catalyst used in the process of this invention must also contain an activatable ligand.
• activatable ligand refers to a ligand, which may be activated by the aluminoxane activating compound (or the aluminoxane compound and eventually a minor portion of a further activating compound to facilitate olefin polymerization).
• Exemplary activatable ligands are independently selected from the group consisting of a hydrogen atom, a halogen atom, a C 1-10 hydrocarbyl radical, a C 1-10 alkoxy radical, a C 5-10 aryl oxide radical; each of which said hydrocarbyl, alkoxy, and aryl oxide radicals may be unsubstituted by or further substituted by a halogen atom, a C 1-8 alkyl radical, a C 1-8 alkoxy radical, a C 6-10 aryl or aryloxy radical, a silicium radical, an amido radical which is unsubstituted or substituted by up to two C 1-8 alkyl radicals; a phosphido radical which is unsubstituted or substituted by up to two C 1-8 alkyl radicals.
• the number of activatable ligands depends upon the valency of the metal and the valency of the activatable ligand.
• the preferred catalyst metals are Group 4 metals in their highest oxidation state (i.e. 4+) and the preferred activatable ligands are monoanionic (such as a hydrocarbyl group - especially methyl).
• the preferred catalyst contains a phosphinimine ligand, a cyclopentadienyl ligand and two chloride (or methyl) ligands bonded to the Group 4 metal.
• the metal of the catalyst component may not be in the highest oxidation state.
• a titanium (III) component would contain only one activatable ligand.
• the most preferred catalysts for use in the process according to the invention are Group 4 organometallic complex in its highest oxidation state having a phosphinimine ligand, a cyclopentadienyl-type ligand and two activatable ligands. These requirements may be concisely described using the following formula for the preferred catalyst: wherein: (a) M is a metal selected from Ti, Hf and Zr; (b) PI is the phosphinimine ligand according to Form. VII as defined above.
• Cp is a ligand selected from the group consisting of cyclopentadienyl, substituted cyclopentadienyl, indenyl, substituted indenyl, fluorenyl, substituted fluorenyl; and (d) X is an activatable ligand.
• Aluminoxanes may be used as co catalysts and/or as a catalyst poison scavenger and/or as an alkylating agent. Most often the aluminoxane is a mixture of different organo aluminum compounds.
• the alumoxane may be of the overall formula: (R 4 ) 2 AlO(R 4 AlO) m Al(R 4 ) 2 wherein each R 4 is independently selected from the group consisting of C 1-20 hydrocarbyl radicals and m is from 0 to 50, preferably R 4 is a C 1-4 radical and m is from 5 to 30.
• Methylalumoxane (or "MAO") in which most of the R groups in the compounds of the mixture are methyl is the preferred alumoxane.
• Alumoxanes are also readily available articles of commerce generally as a solution in a hydrocarbon solvent.
• the alumoxane when employed, is preferably added at an aluminum to transition metal (in the catalyst) mole ratio of from 20:1 to 1000:1. Preferred ratios are from 50:1 to 250:1.
• a sterically bulky compound to enhance catalyst activity in the process of the present invention.
• Sterically bulky amines and/or sterically bulky alcohols are preferred.
• Hindered phenols are most preferred.
• the process of the present invention may be a bulk polymerization process, a solution polymerization process or a slurry polymerization process.
• the process of the present invention preferably is a solution process.
• Solution processes for the polymerization of ethylene propylene elastomers are well known in the art. These processes are conducted in the presence of an inert hydrocarbon solvent such as a C 5-12 hydrocarbon which may be unsubstituted or substituted by a C 1-4 alkyl group such as pentane, methyl pentane, hexane, heptane, octane, cyclohexane, methylcyclohexane and hydrogenated naphtha.
• an inert hydrocarbon solvent such as a C 5-12 hydrocarbon which may be unsubstituted or substituted by a C 1-4 alkyl group
• the process of this invention may be undertaken at a temperature of from 20° C to 150° C.
• a temperature of from 20° C to 150° C As previously noted, the use of a higher polymerization temperature will generally reduce solution viscosity (which is desirable) but also reduce molecular weight (which may be undesirable).
• the monomers used in the process according to the invention for the preparation of the polymer may be dissolved/dispersed in the solvent either prior to being fed to the reactor (or for gaseous monomers the monomer may be fed to the reactor so that it will dissolve in the reaction mixture).
• the solvent and monomers Prior to mixing, are preferably purified to remove potential catalyst poisons such as water or oxygen.
• the feedstock purification follows standard practices in the art, e.g. molecular sieves, alumina beds and oxygen removal catalysts are used for the purification of monomers.
• the solvent itself as well e.g. methyl pentane, cyclohexane, hexane or toluene
• the feedstock may be heated or cooled prior to feeding to the polymerization reactor. Additional monomers and solvent may be added to a second reactor (if employed) and the reactor(s) may be heated or cooled.
• the catalyst components may be added as a separate solutions to the reactor or premixed before adding to the reactor.
• the residence time in the polymerization reactor will depend on the design and the capacity of the reactor. Generally the reactors should be operated under conditions to achieve a thorough mixing of the reactants. If two reactors in series are used, it is preferred that from 50 to 95 weight % of the final polymer is polymerized in the first reactor, with the balance being polymerized in the second reactor. It is also possible to use a dual parallel reactor setup. On leaving the reactor the solvent is removed and the resulting polymer is finished in a conventional manner.
• the invention also relates to the polymer obtainable by the process according to the invention.
• the invention also relates to compounds comprising the polymer obtainable by the process of the present invention, a plasticizer and a filler.
• the polymer Due to the relatively high fraction of the vinyl norbornene non-conjugated diolefins that is polymerized with only one of the double bonds, the polymer comprises a lot of double bonds originating from the vinyl norbornene available for curing. It is known that the double bonds originating from the vinyl norbornene give a high curing speed; especially if a peroxide based curing system is used.
• the polymer of the present invention for the production in peroxide curing processes, preferably for the production of hoses, cable and wire covering, profiles and thermoplastic vulcanizates.
• the polymer obtainable with the process of the present invention may contain monomeric units of one or more ⁇ -olefins having from 3 to for example 23 carbon atoms.
• ⁇ -olefins are propylene, 1-butene, 1-pentene, 1-hexene and 1-octene.
• the polymer contains monomeric units of propylene as the ⁇ -olefin.
• the polymers may have a weight average molecular weight of 10000 to 500000 kg/kmol.
• the polymers Preferably, have a weight average molecular weight of 20000 to 400000 kg/kmol, more preferably 50000 to 300000 kg/kmol.
• the polymer for example contains 0.01 - 20 weight % vinyl norbornene, preferably 0.1 - 10 weight % mol.%, more preferably 0.2 - 6 weight %. Most preferably is a polymer which contains 1-5 weight % vinyl norbornene.
• the preferred vinyl norbornene is 5-vinyl-2-norbornene.
• the polymer exists of ethylene, the ⁇ -olefin and the vinyl norbornene.
• the polymer comprises ethylene, the ⁇ -olefin, the vinyl norbornene and a further non-conjugated diene, for example dicyclopentadiene, 1,4-hexadiene, 5-methylene-2-norbornene and 5-ethylidene-2-norbornene, preferably 5-ethylidene-2-norbornene.
• the polymer comprises at least 0.01 weight % 5-ethylene-2-norbornene, more preferably at least 0.05 weight %.
• the polymer comprises from 40 to 90 weight % of ethylene, from 0.1 to 10 weight % of the non-conjugated dienes, the balance being the ⁇ -olefin.
• the polymer fulfils also the following condition:
• the elastomeric copolymers that were prepared as described in the examples were analyzed by means of Size Exclusion Chromatography and Differential Viscosimetry (SEC-DV) in accordance with the method described in the foregoing. All copolymers were elastomeric and in a DSC analysis they showed no peaks with a peak temperature higher than 25°C.
• composition of the polymers .
• FT-IR Fourier transformation infrared spectroscopy
• ⁇ is, expressed in degrees, calculated from the difference between the phase angle ⁇ at a frequency of 0.1 rad/s and the phase angle ⁇ at a frequency of 100 rad/s.
• ML(1+4) 125° C is the Mooney viscosity, measured at 125° C.
• the polymerization was carried out in one or two solution polymerization reactors in series (with a volume of 3L each).
• the feed streams were purified by contacting with various absorption media to remove catalyst killing impurities such as water, oxygen and polar compounds as is known to those skilled in the art.
• the process is continuous in all feed streams.
• Premixed hexane, propene, ethylene, dienes, hydrogen, aluminoxane and the sterically bulky amines and/or sterically bulky alcohols were precooled before being fed to the (first) reactor.
• the precatalyst prepared according to the method described in US Patent Nr. 6,063,879 and references cited therein and WO-A-02/070569 and listed in table 1, and if applicable t-BF20 borate solution were separately fed to the (first) reactor.
• the polymer solution was continuously removed through a discharge line and worked-up by continuously steam stripping and subsequently a batch wise drying the polymer produced during a well-defined time on a mill.
• Table 1 Explanation of catalyst components.
• Cat 1 Catalyst, ⁇ 5 -(perfluorophenylcyclopentadienyl)(tri- tert -butylphosphinimine) titanium dichloride.
• Cat 2 Catalyst, ⁇ 5 -(perfluorophenylcyclopentadienyl)(tri- tert -butylphosphinimine) titanium dimethyl.
• Cat 3 Catalyst, ⁇ 5 -(cyclopentadienyl)(tri- iso -propylphosphinimine) titanium dimethyl.
• a (very) lower ⁇ value is indicative of the presence of more (highly) branched polymer material.
• Gel formation is related to the presence of more, highly branched material.
• the catalyst has been applied with MMAO-7 as catalyst activator.
• the produced EPDM polymer has a high VNB content and a relatively low degree of branching, in terms of ⁇ of 18.5.
• the polymer of comparative experiment A were BF20 had been applied as catalyst activator, under further similar conditions, had a significant lower VNB content whereas the degree of branching was higher resulting in a lower ⁇ (12.1).
• Example 1 had a single reactor set up (3 L), while example 2 had a two reactor set up in series (3 L + 3 L). In these experiments both EPDM polymers had a high VNB content at a moderate degree of branching ( ⁇ of 18.5 and 15.5).
• comparative experiments A and B BF20 was used as catalyst activator. Comparative experiment A had a one reactor set up (3 L), while comparative experiment B had a two reactor set up in series (3 L + 3 L). In both experiments EPDM polymers were produced with low VNB content, resulting in a higher degree of branching (both with ⁇ of 12.1). Examples 1, as well as examples 3,6 and 7 show that in VNB generally leads to a lower ⁇ .
• an EPDM polymer was produced with an extreme high VNB content (4wt%).
• the applied catalyst activator was MAO.
• Example 4 a EPDM polymer with very high VNB content (3.2) was produced with a MAO activated catalyst.
• a borate-activated catalyst was used under further the same conditions.
• the VNB-content in Example 4 was approximately ten times as high to obtain an equal amount of branching, in terms of ⁇ (9.0 and 8.6).
• examples 5 and 7 two different catalysts according to the invention were used and an activated MAO.
• the VNB content is relatively high (1.3 wt %), while only a moderate degree of branching was obtained ( ⁇ of 20).
• Example 8 (Cat1) at a VNB content of 0.32 wt % a low branching level was obtained ( ⁇ of 30).
• BHEB was used instead of BHT. Also in this case, the VNB content was high (1,4 wt %) without a too high degree of branching ( ⁇ of 13).
• Example 7 versus comparative experiment A.
• MMAO-7 was used.
• the produced EPDM polymer had a low VNB content, resulting in a low degree of branching, in terms of ⁇ of 34.4.
• MMAO-7 was used in combination with Cat 4.
• the produced EPDM polymers had relatively high ⁇ values for their VNB contents.
• Comparative example D demonstrates that a Vanadium based Ziegler Natta catalyst gives relative low ⁇ at low VNB content (0.58 wt %). Compared to example 6 (with 1.42 wt % VNB) a similar ⁇ is obtained at a lower VNB content.

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